JP7482846B2 - Semiconductor photoresist composition and pattern formation method using the same - Google Patents
Semiconductor photoresist composition and pattern formation method using the same Download PDFInfo
- Publication number
- JP7482846B2 JP7482846B2 JP2021183873A JP2021183873A JP7482846B2 JP 7482846 B2 JP7482846 B2 JP 7482846B2 JP 2021183873 A JP2021183873 A JP 2021183873A JP 2021183873 A JP2021183873 A JP 2021183873A JP 7482846 B2 JP7482846 B2 JP 7482846B2
- Authority
- JP
- Japan
- Prior art keywords
- photoresist
- group
- acid
- pattern
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 109
- 239000000203 mixture Substances 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 46
- 239000004065 semiconductor Substances 0.000 title claims description 43
- 230000007261 regionalization Effects 0.000 title description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 49
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 21
- -1 organic acid compound Chemical class 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000059 patterning Methods 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 45
- 230000008569 process Effects 0.000 description 25
- 239000010409 thin film Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 150000007524 organic acids Chemical class 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 125000005842 heteroatom Chemical group 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 11
- 239000007859 condensation product Substances 0.000 description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 125000000304 alkynyl group Chemical group 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 235000005985 organic acids Nutrition 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000001900 extreme ultraviolet lithography Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229960005261 aspartic acid Drugs 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical class N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MFIBZDZRPYQXOM-UHFFFAOYSA-N [dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silyl]oxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](C)(C)O[Si](C)(C)CCCOCC1CO1 MFIBZDZRPYQXOM-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008080 stochastic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2224—Compounds having one or more tin-oxygen linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks
Landscapes
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Description
本発明は半導体フォトレジスト用組成物およびそれを用いたパターン形成方法に関する。 The present invention relates to a semiconductor photoresist composition and a pattern formation method using the same.
次世代の半導体デバイスを製造するための要素技術の一つとして、EUV(極端紫外線)リソグラフィが注目されている。EUVリソグラフィは、露光光源として波長13.5nmのEUV光を用いるパターン形成技術である。EUVリソグラフィによれば、半導体デバイス製造プロセスの露光工程で、きわめて微細なパターン(例えば20nm以下)を形成できることが実証されている。 EUV (extreme ultraviolet) lithography is attracting attention as one of the core technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technology that uses EUV light with a wavelength of 13.5 nm as the exposure light source. It has been demonstrated that EUV lithography can form extremely fine patterns (e.g., 20 nm or less) during the exposure step in the semiconductor device manufacturing process.
極端紫外線(extreme ultraviolet、EUV)リソグラフィの実現は、16nm以下の空間解像度(spatial resolutions)で行い得る互換可能なフォトレジストの現像(development)を必要とする。現在、伝統的な化学増幅型(CA:chemically amplified)フォトレジストは、次世代デバイスのための解像度(resolution)、フォトスピード(photospeed)、フィーチャー粗さ(feature roughness)、およびラインエッジ粗さ(line edge roughnessまたはLER)に対する仕様(specifications)を満たすために、日々研究開発されている。 The realization of extreme ultraviolet (EUV) lithography requires the development of compatible photoresists capable of spatial resolutions of 16 nm or less. Currently, traditional chemically amplified (CA) photoresists are being researched and developed daily to meet the specifications for resolution, photospeed, feature roughness, and line edge roughness (LER) for next generation devices.
このような高分子型フォトレジストで起きる酸触媒反応(acid catalyzed reactions)に起因する固有の像ぶれ(intrinsic image blur)は、小さいフィーチャー(feature)の大きさで解像度を制限するが、これは電子線(e-beam)リソグラフィにおいて長い間知られている事実である。化学増幅型(CA)フォトレジストは、高い感度(sensitivity)のために設計されたが、これらの典型的な元素構成(elemental makeup)が13.5nmの波長ではフォトレジストの吸光度を低下させ、その結果、感度を減少させるので、部分的にはEUV露光下でさらに困難になることがある。 Intrinsic image blur due to acid catalyzed reactions in such polymeric photoresists limits resolution at small feature sizes, a fact that has long been known in e-beam lithography. Chemically amplified (CA) photoresists were designed for high sensitivity but can be more difficult under EUV exposure in part because their typical elemental makeup reduces the absorbance of the photoresist at 13.5 nm wavelengths, thereby reducing sensitivity.
CAフォトレジストはまた、小さいフィーチャーの大きさで粗さ(roughness)イシューによる困難性があり、部分的に酸触媒工程の本質に起因し、フォトスピード(photospeed)が減少することによって、ラインエッジ粗さ(LER)が増加することが実験により示された。CAフォトレジストの欠点および問題に起因して、半導体産業では新たな類型の高性能フォトレジストに対する要求がある。 CA photoresists also have difficulty with roughness issues at small feature sizes, and experiments have shown that line edge roughness (LER) increases as photospeed decreases, due in part to the nature of the acid catalyzed process. Due to the shortcomings and problems of CA photoresists, there is a demand in the semiconductor industry for a new class of high performance photoresists.
上記で説明した化学増幅型フォトレジスト組成物の欠点を克服するために、無機系感光性組成物が研究されてきた。無機系感光性組成物の場合、主に非化学増幅型メカニズムによる化学的変性により、現像剤組成物による除去に耐性を有するネガティブトーンパターニングに使用される。無機系組成物の場合、炭化水素に比べて高いEUV吸収率を有する無機系元素を含有しており、非化学増幅型メカニズムによっても感度を確保することができ、確率的な効果に対しても感度は低く、ラインエッジ粗さおよび欠陥数も少ないと知られている。 In order to overcome the drawbacks of the chemically amplified photoresist composition described above, inorganic photosensitive compositions have been researched. Inorganic photosensitive compositions are mainly used for negative tone patterning, which is resistant to removal by developer compositions due to chemical modification by a non-chemically amplified mechanism. Inorganic compositions contain inorganic elements with higher EUV absorption rates than hydrocarbons, and are known to ensure sensitivity even through a non-chemically amplified mechanism, have low sensitivity to stochastic effects, and have low line edge roughness and number of defects.
タングステン、ニオブ(niobium)、チタン(titanium)、および/またはタンタル(tantalum)と混合されたタングステンのペルオキソポリ酸(peroxopolyacids)に基づいた無機フォトレジストは、パターニングのための放射感受性材料(radiation sensitive materials)用として報告されてきた(特許文献1および非特許文献1参照)。 Inorganic photoresists based on peroxopolyacids of tungsten mixed with tungsten, niobium, titanium, and/or tantalum have been reported for patterning radiation sensitive materials (see US Pat. No. 5,399,313 and Non-Patent Document 1).
これらの材料は遠紫外線(deep UV)、X線、および電子線ソースであって、二重層構成(bilayer configuration)に大きなフィーチャーをパターニングすることにおいて効果的であった。さらに最近では、プロジェクションEUV露光によって、15nmハーフピッチ(HP)を現像するために、ペルオキソ錯化剤(peroxo complexing agent)とともに陽イオンハフニウムメタルオキシドサルフェート(cationic hafnium metal oxide sulfate,HfSOx)材料を使用する場合は印象的な性能を示した(特許文献2および非特許文献2参照)。このシステムは、非CAフォトレジスト(non-CA photoresist)の最上の性能を示し、実行可能なEUVフォトレジストのための要件に近いフォトスピードを有する。しかし、ペルオキソ錯化剤を有するハフニウムメタルオキシドサルフェート材料(hafnium metal oxide sulfate materials)はいくつかの現実的な欠点を有する。第1に、この材料は高い腐食性の硫酸/過酸化水素混合物でコートされ、保存安定性が良くない。第2に、複合混合物として性能改善のための構造変更が容易でない。第3に、25重量%程度のきわめて高い濃度のTMAH(tetramethylammonium hydroxide)溶液などで現像されなければならない。 These materials have been effective in patterning large features in bilayer configurations with deep UV, x-ray, and e-beam sources. More recently, impressive performance has been shown when using cationic hafnium metal oxide sulfate (HfSOx) materials with peroxo complexing agents to develop 15 nm half pitch (HP) by projection EUV exposure (see U.S. Pat. No. 5,393,311 and U.S. Pat. No. 5,433,631). This system shows the best performance of non-CA photoresists and has a photospeed approaching the requirements for a viable EUV photoresist. However, hafnium metal oxide sulfate materials with peroxo complexing agents have several practical drawbacks. First, the material is coated with a highly corrosive sulfuric acid/hydrogen peroxide mixture and has poor storage stability. Second, as a complex mixture, it is not easy to modify the structure to improve performance. Third, it must be developed with a very high concentration of TMAH (tetramethylammonium hydroxide) solution, such as 25% by weight.
最近では、スズを含む分子が極端紫外線の吸収に優れることが知られてから活発な研究がなされている。その1つである有機スズ高分子の場合、光吸収またはこれによって生成された二次電子によってアルキル配位子が解離することにより、周辺鎖とのオキソ結合による架橋によって、有機系現像液で除去されないネガティブトーンパターニングが可能である。 Recently, active research has been conducted on molecules containing tin since it was discovered that they have excellent extreme ultraviolet absorption. In the case of organotin polymers, one of these, alkyl ligands are dissociated by light absorption or the secondary electrons generated by it, and crosslinking with surrounding chains through oxo bonds enables negative tone patterning that is not removed by organic developers.
ただし、このような有機スズ系のフォトレジストは水分に敏感である短所がある。 However, these organotin photoresists have the disadvantage of being sensitive to moisture.
本発明の一実施形態は、保存安定性および感度特性に優れた半導体フォトレジスト用組成物を提供する。 One embodiment of the present invention provides a composition for semiconductor photoresists that has excellent storage stability and sensitivity characteristics.
本発明の他の実施形態は、上記半導体フォトレジスト用組成物を用いたパターン形成方法を提供する。 Another embodiment of the present invention provides a pattern formation method using the semiconductor photoresist composition.
本発明の一実施形態による半導体フォトレジスト用組成物は、下記化学式1で表される有機スズ化合物と、置換された有機酸、少なくとも2個の酸官能基を含む有機酸、および置換または非置換のスルホン酸からなる群より選択される少なくとも1種の有機酸化合物との縮合物;ならびに溶媒を含む。 A composition for semiconductor photoresist according to one embodiment of the present invention includes a condensate of an organotin compound represented by the following chemical formula 1 with at least one organic acid compound selected from the group consisting of substituted organic acids, organic acids containing at least two acid functional groups, and substituted or unsubstituted sulfonic acids; and a solvent.
前記化学式1において、
R1は、置換もしくは非置換の炭素数1~20のアルキル基、置換もしくは非置換の炭素数3~20のシクロアルキル基、置換もしくは非置換の炭素数2~20のアルケニル基、置換もしくは非置換の炭素数2~20のアルキニル基、置換もしくは非置換の炭素数6~30のアリール基、または-L-O-Rdであり、
Ra、RbおよびRcは、それぞれ独立して、置換もしくは非置換の炭素数1~20のアルキル基、置換もしくは非置換の炭素数3~20のシクロアルキル基、置換もしくは非置換の炭素数2~20のアルケニル基、置換もしくは非置換の炭素数2~20のアルキニル基、置換もしくは非置換の炭素数6~30のアリール基、またはこれらの組み合わせであり、
Lは、単結合、または置換もしくは非置換の炭素数1~20のアルキレン基であり、
Rdは、置換または非置換の炭素数1~20のアルキル基である。
In the above Chemical Formula 1,
R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or -L-O-R d ;
R a , R b and R c each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof;
L is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms;
R d is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
上記縮合物は、上記有機スズ化合物由来の構成単位および上記有機酸化合物由来の構成単位を、85:15~99:1の質量比で含み得る。 The condensate may contain constituent units derived from the organotin compound and constituent units derived from the organic acid compound in a mass ratio of 85:15 to 99:1.
上記置換された有機酸は、ヘテロ原子、ヘテロ原子を含む原子団、およびこれらの組み合わせからなる群より選択される少なくとも1種で置換され、上記ヘテロ原子は、硫黄原子(S)、窒素原子(N)、酸素原子(O)、リン原子(P)、およびフッ素原子(F)からなる群より選択される少なくとも1種であり、上記ヘテロ原子を含む原子団は、-OH、-SH、-NH2、-S-および-S-S-からなる群より選択される少なくとも1種であり得る。 The substituted organic acid is substituted with at least one selected from the group consisting of a heteroatom, an atomic group containing a heteroatom, and a combination thereof, the heteroatom being at least one selected from the group consisting of a sulfur atom (S), a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), and a fluorine atom (F), and the atomic group containing a heteroatom can be at least one selected from the group consisting of -OH, -SH, -NH 2 , -S-, and -S-S-.
上記有機酸化合物は、グリコール酸、マロン酸、コハク酸、1,2,3,4-ブタンテトラカルボン酸、クエン酸、酒石酸、トリカルバリル酸、乳酸、チオグリコール酸、ジチオジグリコール酸、チオジグリコール酸、フタル酸、マレイン酸、L-アスパラギン酸、p-トルエンスルホン酸、メチルスルホン酸、およびベンゼンスルホン酸からなる群より選択される少なくとも1種であり得る。 The organic acid compound may be at least one selected from the group consisting of glycolic acid, malonic acid, succinic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, tartaric acid, tricarballylic acid, lactic acid, thioglycolic acid, dithiodiglycolic acid, thiodiglycolic acid, phthalic acid, maleic acid, L-aspartic acid, p-toluenesulfonic acid, methylsulfonic acid, and benzenesulfonic acid.
上記有機酸化合物のpKaは、5以下であり得る。 The pKa of the organic acid compound may be 5 or less.
上記縮合物はオリゴマー、ポリマーおよびこれらの組み合わせのうち少なくとも一つであり得る。 The condensate may be at least one of an oligomer, a polymer, and a combination thereof.
上記縮合物は加水分解縮合物を含み得る。 The above condensation product may include a hydrolysis condensation product.
上記半導体フォトレジスト用組成物は、界面活性剤、架橋剤、レベリング剤、またはこれらの組み合わせの添加剤をさらに含み得る。 The semiconductor photoresist composition may further include additives such as a surfactant, a crosslinking agent, a leveling agent, or a combination thereof.
本発明の他の実施形態によるパターン形成方法は、基板上にエッチング対象膜を形成する工程、前記エッチング対象膜上に前述した半導体フォトレジスト用組成物を塗布してフォトレジスト膜を形成する工程、前記フォトレジスト膜をパターニングしてフォトレジストパターンを形成する工程、および前記フォトレジストパターンをエッチングマスクとして用いて前記エッチング対象膜をエッチングする工程を含む。 A method for forming a pattern according to another embodiment of the present invention includes the steps of forming a film to be etched on a substrate, applying the above-described semiconductor photoresist composition onto the film to be etched to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.
上記フォトレジストパターンを形成する工程は、5~150nmの波長範囲の光を使用し得る。 The process for forming the photoresist pattern may use light in the wavelength range of 5 to 150 nm.
上記パターン形成方法は、上記基板と上記フォトレジスト膜との間に形成されるレジスト下層膜を形成する工程をさらに含み得る。 The pattern forming method may further include a step of forming a resist underlayer film between the substrate and the photoresist film.
上記フォトレジストパターンは、5nm~100nmの幅を有し得る。 The photoresist pattern may have a width of 5 nm to 100 nm.
本発明によれば、保存安定性および感度特性に優れた半導体フォトレジスト用組成物が提供される。 The present invention provides a semiconductor photoresist composition that has excellent storage stability and sensitivity characteristics.
以下、添付する図面を参照して本発明の実施形態を詳細に説明すると、以下のとおりである。ただし、本発明を説明するにあたり、既に公知の機能あるいは構成に係る説明は、本発明の要旨を明瞭にするために省略する。 The following is a detailed description of an embodiment of the present invention with reference to the attached drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted in order to clarify the gist of the present invention.
本発明を明確に説明するために、説明と関係ない部分を省略し、明細書全体にわたって同一または類似の構成要素に対しては同じ参照符号を付ける。また、図面に示す各構成の大きさおよび厚さは、説明の便宜上任意に示したので、本発明は必ずしも示されたところに限定されない。 In order to clearly explain the present invention, parts that are not relevant to the explanation will be omitted, and the same or similar components will be given the same reference numerals throughout the specification. In addition, the size and thickness of each component shown in the drawings are shown arbitrarily for the convenience of explanation, and the present invention is not necessarily limited to what is shown.
図面において、複数の層および領域を明確に表現するために厚さを誇張して示した。そして、図面において、説明の便宜上、一部の層および領域の厚さを誇張して示した。層、膜、領域、板などの部分が他の部分「上に」または「の上に」あるというとき、これは、他の部分の「すぐ上に」ある場合だけでなく、その中間にまた他の部分がある場合も含む。 In the drawings, the thickness of multiple layers and regions is exaggerated to clearly show them. Also, in the drawings, the thickness of some layers and regions is exaggerated for the convenience of explanation. When a layer, film, region, plate, etc. is said to be "on" or "above" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part between them.
本明細書において、「置換」とは、水素原子が重水素原子、ハロゲン原子、ヒドロキシ基、アミノ基、置換もしくは非置換の炭素数1~30のアルキルアミノ基、ニトロ基、置換もしくは非置換の炭素数1~40のシリル基(例えば炭素数1~10のアルキルシリル基)、炭素数1~30のアルキル基、炭素数1~10のハロアルキル基、炭素数3~30のシクロアルキル基、炭素数6~30のアリール基、炭素数1~20のアルコキシ基、またはシアノ基に置換されたことを意味する。本明細書において、「非置換」とは、水素原子が他の置換基に置換されずに水素原子として残っていることを意味する。 In this specification, "substituted" means that a hydrogen atom is replaced with a deuterium atom, a halogen atom, a hydroxy group, an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a nitro group, a substituted or unsubstituted silyl group having 1 to 40 carbon atoms (e.g., an alkylsilyl group having 1 to 10 carbon atoms), an alkyl group having 1 to 30 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. In this specification, "unsubstituted" means that a hydrogen atom remains as a hydrogen atom without being replaced with another substituent.
本明細書において、「アルキル(alkyl)基」とは、別段の定義がない限り、直鎖状または分枝鎖状の脂肪族炭化水素基を意味する。アルキル基はいかなる二重結合や三重結合をも含んでいない「飽和アルキル(saturated alkyl)基」であり得る。 As used herein, unless otherwise defined, an "alkyl group" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.
上記アルキル基は、炭素数1~20のアルキル基であり得る。より具体的には、アルキル基は、炭素数1~10のアルキル基または炭素数1~6のアルキル基でもあり得る。例えば、炭素数1~4のアルキル基は、アルキル鎖に1~4個の炭素原子が含まれることを意味し、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、およびt-ブチル基からなる群より選択される基であることを示す。 The alkyl group may be an alkyl group having 1 to 20 carbon atoms. More specifically, the alkyl group may be an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 6 carbon atoms. For example, an alkyl group having 1 to 4 carbon atoms means that the alkyl chain contains 1 to 4 carbon atoms, and indicates a group selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.
上記アルキル基の具体的な例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t-ブチル基、ペンチル基、ヘキシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などを意味する。 Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
本明細書において、「シクロアルキル(cycloalkyl)基」とは、別段の定義がない限り、1価の環状脂肪族炭化水素基を意味する。 In this specification, unless otherwise defined, a "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.
本明細書において、「アルケニル(alkenyl)基」とは、別段の定義がない限り、直鎖状または分枝鎖状の脂肪族炭化水素基として、1つ以上の二重結合を含む脂肪族不飽和アルケニル(unsaturated alkenyl)基を意味する。 In this specification, unless otherwise defined, an "alkenyl group" refers to an aliphatic unsaturated alkenyl group that contains one or more double bonds as a linear or branched aliphatic hydrocarbon group.
本明細書において、「アルキニル(alkynyl)基」とは、別段の定義がない限り、直鎖状または分枝鎖状の脂肪族炭化水素基として、1つ以上の三重結合を含む脂肪族不飽和アルキニル(unsaturated alkynyl)基を意味する。 In this specification, unless otherwise defined, an "alkynyl group" refers to an aliphatic unsaturated alkynyl group that contains one or more triple bonds as a linear or branched aliphatic hydrocarbon group.
本明細書において、「アリール(aryl)基」とは、環状の置換基のすべての元素がp-軌道を有しており、これらp-軌道が共役(conjugation)を形成している置換基を意味し、単環または縮合多環(すなわち、炭素原子の隣接する対を分け合う環)官能基を含む。 As used herein, the term "aryl group" refers to a cyclic substituent in which all elements have p-orbitals and these p-orbitals form conjugation, including monocyclic or fused polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.
以下、本発明の一実施形態による半導体フォトレジスト用組成物を説明する。 The following describes a semiconductor photoresist composition according to one embodiment of the present invention.
本発明の一実施形態による半導体フォトレジスト用組成物は、縮合物および溶媒を含み、上記縮合物は下記化学式1で表される有機スズ化合物と、置換された有機酸、少なくとも2個の酸官能基を含む有機酸、および置換または非置換のスルホン酸からなる群より選択される少なくとも1種の有機酸化合物と、の縮合物である。 A composition for semiconductor photoresist according to one embodiment of the present invention includes a condensate and a solvent, and the condensate is a condensate of an organotin compound represented by the following chemical formula 1 and at least one organic acid compound selected from the group consisting of substituted organic acids, organic acids containing at least two acid functional groups, and substituted or unsubstituted sulfonic acids.
上記化学式1において、
R1は、置換もしくは非置換の炭素数1~20のアルキル基、置換もしくは非置換の炭素数3~20のシクロアルキル基、置換もしくは非置換の炭素数2~20のアルケニル基、置換もしくは非置換の炭素数2~20のアルキニル基、置換もしくは非置換の炭素数6~30のアリール基、または-L-O-Rdであり、
Ra、Rb、およびRcは、それぞれ独立して、置換もしくは非置換の炭素数1~20のアルキル基、置換もしくは非置換の炭素数3~20のシクロアルキル基、置換もしくは非置換の炭素数2~20のアルケニル基、置換もしくは非置換の炭素数2~20のアルキニル基、置換もしくは非置換の炭素数6~30のアリール基、またはこれらの組み合わせであり、
Lは、単結合、または置換もしくは非置換の炭素数1~20のアルキレン基であり、
Rdは、置換または非置換の炭素数1~20のアルキル基である。
In the above Chemical Formula 1,
R 1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or -L-O-R d ;
R a , R b , and R c each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a combination thereof;
L is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms;
R d is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
本明細書において、縮合物とは、縮合反応によって生成される生成物を通称するものとして、上記縮合反応とは、少なくとも2個の有機化合物分子が活性原子または原子団を中心に結合されることにより、水、アンモニア、塩化水素などの単分子を放出する反応を意味する。ここでは、2個の分子が単に結合することにより生成される化合物も縮合物の範疇に含む。 In this specification, the term "condensate" is used to refer to a product produced by a condensation reaction, and the condensation reaction refers to a reaction in which at least two organic compound molecules are bonded to an active atom or atomic group at the center, thereby releasing a single molecule such as water, ammonia, or hydrogen chloride. Here, compounds produced by simply bonding two molecules are also included in the category of condensates.
上記生成物は、モノマー、オリゴマー、ポリマー、およびこれらの組み合わせが含まれ得る。 The products may include monomers, oligomers, polymers, and combinations thereof.
本発明の一実施形態として、上記化学式1のR1は、置換もしくは非置換の炭素数1~20のアルキル基、置換もしくは非置換の炭素数2~20のアルケニル基、置換もしくは非置換の炭素数2~20のアルキニル基、またはこれらの組み合わせであり得る。 As one embodiment of the present invention, R 1 in the above Chemical Formula 1 may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
具体的な例として、上記化学式1のR1は、置換または非置換の炭素数3~20のアルキル基であり得る。 As a specific example, R 1 in the above formula 1 may be a substituted or unsubstituted alkyl group having 3 to 20 carbon atoms.
例えば、上記化学式1のR1は、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、またはこれらの組み合わせであり得る。 For example, R 1 in Formula 1 above can be an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, or a combination thereof.
例として、上記化学式1のRa、Rb、およびRcは、それぞれ独立して、置換もしくは非置換の炭素数1~20のアルキル基、置換もしくは非置換の炭素数2~20のアルケニル基、置換もしくは非置換の炭素数2~20のアルキニル基、またはこれらの組み合わせであり得る。 For example, R a , R b , and R c in the above Chemical Formula 1 can each independently be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
例えば、Ra、Rb、およびRcは、それぞれ独立して、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、エテニル基、またはこれらの組み合わせであり得る。 For example, R a , R b , and R c can each independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an ethenyl group, or a combination thereof.
上記Ra、Rb、およびRcは、それぞれ同一であってもよいし異なっていてもよい。 The above R a , R b and R c may be the same or different.
例として、上記置換された有機酸は、ヘテロ原子、ヘテロ原子を含む原子団、およびこれらの組み合わせのうち少なくとも一つに置換され、
上記ヘテロ原子は、硫黄原子(S)、窒素原子(N)、酸素原子(O)、リン原子(P)、およびフッ素原子(F)からなる群より選択されるの少なくとも1種であり、
上記ヘテロ原子を含む原子団は、-OH、-SH、-NH2、-S-および-S-S-からなる群より選択される少なくとも1種であり得る。
By way of example, the substituted organic acid may be substituted with at least one of a heteroatom, a group of atoms that includes a heteroatom, and combinations thereof;
The heteroatom is at least one selected from the group consisting of a sulfur atom (S), a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), and a fluorine atom (F);
The atomic group containing a heteroatom may be at least one selected from the group consisting of -OH, -SH, -NH 2 , -S-, and -S-S-.
本明細書における置換された有機酸とは、例えば1個の酸官能基を含み、かつ酸官能基が連結される炭化水素鎖に含まれる炭素原子および水素原子のうち少なくとも1種がヘテロ原子、ヘテロ原子を含む原子団、およびこれらの組み合わせのうち少なくとも1種で置換されたものを意味する。 In this specification, a substituted organic acid means, for example, an organic acid that contains one acid functional group and in which at least one of the carbon atoms and hydrogen atoms contained in the hydrocarbon chain to which the acid functional group is linked is substituted with at least one of a heteroatom, an atomic group containing a heteroatom, or a combination thereof.
例えば、置換された有機酸は、酸官能基が連結される炭化水素鎖の末端に位置する炭素原子および水素原子のうち少なくとも1種、炭化水素鎖の中間に位置する炭素原子および水素原子のうち少なくとも1種、およびこれらの組み合わせのうち少なくとも1種がヘテロ原子、ヘテロ原子を含む原子団、およびこれらの組み合わせのうち少なくとも1種で置換されうる。 For example, in a substituted organic acid, at least one of the carbon and hydrogen atoms located at the end of the hydrocarbon chain to which the acid functional group is linked, at least one of the carbon and hydrogen atoms located in the middle of the hydrocarbon chain, and at least one combination thereof may be substituted with at least one heteroatom, an atomic group containing a heteroatom, and at least one combination thereof.
上記置換された有機酸の例としては、グリコール酸、乳酸、チオグリコール酸、L-アスパラギン酸などが挙げられる。 Examples of the substituted organic acids include glycolic acid, lactic acid, thioglycolic acid, and L-aspartic acid.
本明細書における酸官能基とは、例えばカルボキシル基であり得る。 In this specification, the acid functional group may be, for example, a carboxyl group.
上記の少なくとも2個の酸官能基を含む有機酸は、例えば酸官能基を2個~4個含む有機酸であり得る。このような有機酸の例としては、マロン酸、コハク酸、1,2,3,4-ブタンテトラカルボン酸、クエン酸、酒石酸、トリカルバリル酸、ジチオジグリコール酸、チオジグリコール酸、フタル酸、およびマレイン酸などが挙げられる。 The organic acid containing at least two acid functional groups may be, for example, an organic acid containing 2 to 4 acid functional groups. Examples of such organic acids include malonic acid, succinic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, tartaric acid, tricarballylic acid, dithiodiglycolic acid, thiodiglycolic acid, phthalic acid, and maleic acid.
一方、本明細書における置換または非置換のスルホン酸とは、少なくとも1つの-S(O)2OH基を含む有機酸を意味する。 On the other hand, a substituted or unsubstituted sulfonic acid as used herein means an organic acid containing at least one -S(O) 2 OH group.
置換または非置換のスルホン酸の例としては、p-トルエンスルホン酸、メチルスルホン酸、およびベンゼンスルホン酸などが挙げられる。 Examples of substituted or unsubstituted sulfonic acids include p-toluenesulfonic acid, methylsulfonic acid, and benzenesulfonic acid.
一方、上記有機酸化合物のpKaは5以下、例えば4以下であり得る。 On the other hand, the pKa of the organic acid compound may be 5 or less, for example 4 or less.
pKaは、水溶液内で酸(HA)がH+とA-に解離するときの酸解離定数であるKaにマイナスログ(-log)を取った値であり、pKa値が大きくなるほど当該酸はさらに弱酸であることを意味する。1つの有機酸分子内に2個以上の酸解離官能基が存在する場合、該当分子のpKa値は、pKaが最も低い官能基の値に決定される。 pKa is the negative logarithm (-log) of Ka, which is the acid dissociation constant when an acid (HA) dissociates into H + and A- in an aqueous solution, and the larger the pKa value, the weaker the acid is. When two or more acid dissociable functional groups exist in one organic acid molecule, the pKa value of the molecule is determined to be the value of the functional group with the lowest pKa.
有機酸化合物のpKa値が上記の範囲である場合、有機スズ化合物との縮合物形成が容易であり、得られる縮合物は、オリゴマー以上の高分子で形成されることにより外部の水分の浸透力が減少し得る。 When the pKa value of the organic acid compound is within the above range, it is easy to form a condensation product with the organotin compound, and the resulting condensation product is formed as an oligomer or higher polymer, which can reduce the penetration ability of external moisture.
そのため、上記化学式1で表される有機スズ化合物、および有機酸化合物が縮合反応して形成された縮合物を含む半導体フォトレジスト組成物の保存安定性に優れる。 Therefore, the storage stability of the semiconductor photoresist composition containing the organotin compound represented by the above chemical formula 1 and the condensate formed by the condensation reaction of the organic acid compound is excellent.
上記化学式1で表される有機スズ化合物、および有機酸化合物が縮合反応して形成された縮合物内で、上記有機酸化合物から誘導される基はリガンドの役割を果たし、かつ有機スズ化合物を連結させ、そのため最終生成物としての縮合物は、オリゴマー、ポリマーおよびこれらの組み合わせのうち少なくとも1つであり得る。 In the condensation product formed by the condensation reaction of the organotin compound represented by the above chemical formula 1 and the organic acid compound, the group derived from the organic acid compound acts as a ligand and links the organotin compound, so that the final condensation product can be at least one of an oligomer, a polymer, and a combination thereof.
例として、上記縮合物は加水分解縮合物を含み得る。 For example, the condensation product may include a hydrolysis condensation product.
上記縮合物は、上記有機スズ化合物由来の構成単位および上記有機酸化合物由来の構成単位を85:15~99:1の質量比で含み得る。質量比がこのような範囲であるとき、膜形成特性、溶解性、屈折率、および現像液に対する溶解速度などでより有利である。 The condensate may contain the structural units derived from the organotin compound and the structural units derived from the organic acid compound in a mass ratio of 85:15 to 99:1. When the mass ratio is in this range, it is more advantageous in terms of film-forming properties, solubility, refractive index, and dissolution rate in a developer.
例として、上記縮合物は、上記有機スズ化合物および上記有機酸化合物を、90:10~99:1の質量比で含み得る。具体的には、90:10~97:3の質量比で含み得る。 For example, the condensate may contain the organotin compound and the organic acid compound in a mass ratio of 90:10 to 99:1. Specifically, the mass ratio may be 90:10 to 97:3.
また、上記縮合物は、1,000~30,000g/molの重量平均分子量(Mw)を有することができ、例として1,000~20,000g/molであり得、他の例としては1,000~10,000g/molであり得る。重量平均分子量が上記の範囲であるとき、膜形成特性、溶解性、屈折率および現像液に対する溶解速度などにおいてより有利である。なお、当該重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)により、測定することができる。 The condensate may have a weight average molecular weight (Mw) of 1,000 to 30,000 g/mol, for example 1,000 to 20,000 g/mol, and another example 1,000 to 10,000 g/mol. When the weight average molecular weight is in the above range, it is more advantageous in terms of film forming properties, solubility, refractive index, and dissolution rate in a developer. The weight average molecular weight can be measured by gel permeation chromatography (GPC).
上記縮合物を得る条件は、特に制限されるものではない。 The conditions for obtaining the above condensation product are not particularly limited.
例えば、上記化学式1で表される有機スズ化合物および上記有機酸化合物を、PGMEA(プロピレングリコールモノメチルエーテルアセテート)、エタノール、2-プロパノール、アセトン、酢酸ブチルなどの溶媒に希釈し、必要に応じて反応に必要な水と触媒としての酸(塩酸、酢酸、硝酸など)を加えた後攪拌して、縮重合反応を完結することによって、目的とする縮合物を得ることができる。 For example, the organotin compound represented by the above chemical formula 1 and the above organic acid compound can be diluted in a solvent such as PGMEA (propylene glycol monomethyl ether acetate), ethanol, 2-propanol, acetone, or butyl acetate, and water required for the reaction and an acid as a catalyst (hydrochloric acid, acetic acid, nitric acid, etc.) can be added as necessary, followed by stirring to complete the condensation polymerization reaction, thereby obtaining the desired condensation product.
ここで使用される溶媒、酸または塩基触媒の種類や量は制限なく、任意に選択してもよい。必要な反応時間は、反応物の種類や濃度、反応温度などに応じて多様であるが、通常15分~30日の時間である。しかし、反応時間はこのような範囲に制限されるものではない。 The type and amount of the solvent, acid or base catalyst used here are not limited and may be selected as desired. The required reaction time varies depending on the type and concentration of the reactants, reaction temperature, etc., but is usually 15 minutes to 30 days. However, the reaction time is not limited to such ranges.
一般に使用されるフォトレジスト組成物の場合、エッチング耐性が不足して高いアスペクト比(縦横比)によりパターンが崩れる恐れがある。 Commonly used photoresist compositions lack etching resistance, and there is a risk of pattern collapse due to high aspect ratios.
一方、本発明の一実施形態による半導体フォトレジスト用組成物は、前述の縮合物と溶媒とを含むことが好ましい。 Meanwhile, a composition for semiconductor photoresist according to one embodiment of the present invention preferably contains the above-mentioned condensate and a solvent.
本発明の一実施形態による半導体フォトレジスト組成物に含まれる溶媒は、有機溶媒であり得、例として、芳香族化合物類(例えば、キシレン、トルエン)、アルコール類(例えば、4-メチル-2-ペンタノール、4-メチル-2-プロパノール、1-ブタノール、メタノール、イソプロピルアルコール、1-プロパノール、プロピレングリコールモノメチルエーテル)、エーテル類(例えば、アニソール、テトラヒドロフラン)、エステル類(n-ブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチルアセテート、エチルラクテート)、ケトン類(例えば、メチルエチルケトン、2-ヘプタノン)、これらの混合物などを含み得るが、これらに限定されるものではない。 The solvent contained in the semiconductor photoresist composition according to one embodiment of the present invention may be an organic solvent, and examples thereof may include, but are not limited to, aromatic compounds (e.g., xylene, toluene), alcohols (e.g., 4-methyl-2-pentanol, 4-methyl-2-propanol, 1-butanol, methanol, isopropyl alcohol, 1-propanol, propylene glycol monomethyl ether), ethers (e.g., anisole, tetrahydrofuran), esters (n-butyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), ketones (e.g., methyl ethyl ketone, 2-heptanone), mixtures thereof, and the like.
本発明の一実施形態による半導体フォトレジスト用組成物は、場合によって添加剤をさらに含み得る。添加剤の例としては、界面活性剤、架橋剤、レベリング剤またはこれらの組み合わせが挙げられる。 The semiconductor photoresist composition according to one embodiment of the present invention may further include additives, as needed. Examples of additives include surfactants, crosslinking agents, leveling agents, or combinations thereof.
界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキルピリジニウム塩、ポリエチレングリコール、第4級アンモニウム塩、またはこれらの組み合わせを使用できるが、これらに限定されるものではない。 Examples of surfactants that can be used include, but are not limited to, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, quaternary ammonium salts, or combinations thereof.
架橋剤としては、例えば、メラミン系架橋剤、置換尿素系架橋剤、アクリル系架橋剤、エポキシ系架橋剤、またはポリマー系架橋剤などが挙げられるが、これらに限定されるものではない。少なくとも2個の架橋形成置換基を有する架橋剤として、例えば、メトキシメチル化グリコールウリル、ブトキシメチル化グリコールウリル、メトキシメチル化メラミン、ブトキシメチル化メラミン、メトキシメチル化ベンゾグアナミン、ブトキシメチル化ベンゾグアナミン、4-ヒドロキシブチルアクリレート、アクリル酸、ウレタンアクリレート、アクリルメタクリレート、1,4-ブタンジオールジグリシジルエーテル、グリシドール、ジグリシジル1,2-シクロヘキサンジカルボキシレート、トリメチルプロパントリグリシジルエーテル、1,3-ビス(グリシドキシプロピル)テトラメチルジシロキサン、メトキシメチル化尿素、ブトキシメチル化尿素、またはメトキシメチル化チオ尿素などの化合物を使用することができる。 Examples of crosslinking agents include, but are not limited to, melamine-based crosslinking agents, substituted urea-based crosslinking agents, acrylic-based crosslinking agents, epoxy-based crosslinking agents, and polymer-based crosslinking agents. Examples of crosslinking agents having at least two crosslink-forming substituents include compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, 4-hydroxybutyl acrylate, acrylic acid, urethane acrylate, acrylic methacrylate, 1,4-butanediol diglycidyl ether, glycidol, diglycidyl 1,2-cyclohexanedicarboxylate, trimethylpropane triglycidyl ether, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, methoxymethylated urea, butoxymethylated urea, and methoxymethylated thiourea.
レベリング剤は、印刷時の塗膜平坦性を向上させるためのものであり、商業的な方法で入手可能な公知のレベリング剤を使用することができる。 The leveling agent is used to improve the flatness of the coating film during printing, and any known leveling agent that is commercially available can be used.
これらの添加剤の使用量は、所望の物性によって容易に調節することができ、省略することもできる。 The amount of these additives used can be easily adjusted depending on the desired physical properties, and they can also be omitted.
また、本発明に係る半導体レジスト用組成物は、基板との密着力などの向上のために(例えば、半導体レジスト用組成物の基板との接着力向上のために)、接着力向上剤として、シランカップリング剤を添加剤として使用することができる。シランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリクロロシラン、ビニルトリス(β-メトキシエトキシ)シラン;または3-メタクリロキシプロピルトリメトキシシラン、3-アクリルオキシプロピルトリメトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン;トリメトキシ[3-(フェニルアミノ)プロピル]シランなどの炭素-炭素不飽和結合含有シラン化合物などを使用できるが、これらに限定されるものではない。 In addition, the semiconductor resist composition according to the present invention can use a silane coupling agent as an additive to improve adhesion to a substrate (for example, to improve the adhesive strength of the semiconductor resist composition to a substrate). Examples of the silane coupling agent include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane; or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; and silane compounds containing carbon-carbon unsaturated bonds such as trimethoxy[3-(phenylamino)propyl]silane.
本発明の半導体フォトレジスト用組成物によれば、高いアスペクト比を有するパターンを形成してもパターン崩れが発生しない。したがって、例えば、5~100nmの幅を有する微細パターン、例えば、5~80nmの幅を有する微細パターン、例えば、5~70nmの幅を有する微細パターン、例えば、5~50nmの幅を有する微細パターン、例えば、5~40nmの幅を有する微細パターン、例えば、5~30nmの幅を有する微細パターン、例えば、5~20nmの幅を有する微細パターンを形成するために、5~150nmの波長範囲の光を使用するフォトレジスト工程、例えば、5~100nmの波長範囲の光を使用するフォトレジスト工程、例えば、5~80nmの波長範囲の光を使用するフォトレジスト工程、例えば、5~50nmの波長範囲の光を使用するフォトレジスト工程、例えば、5~30nmの波長範囲の光を使用するフォトレジスト工程、例えば、5~20nmの波長範囲の光を使用するフォトレジスト工程に使用することができる。したがって、本発明の一実施形態による半導体フォトレジスト用組成物を用いると、13.5nm波長のEUV光源を使用する極端紫外線リソグラフィを実現することができる。 According to the semiconductor photoresist composition of the present invention, even if a pattern having a high aspect ratio is formed, the pattern does not collapse. Therefore, in order to form a fine pattern having a width of, for example, 5 to 100 nm, for example, a fine pattern having a width of 5 to 80 nm, for example, a fine pattern having a width of 5 to 70 nm, for example, a fine pattern having a width of 5 to 50 nm, for example, a fine pattern having a width of 5 to 40 nm, for example, a fine pattern having a width of 5 to 30 nm, for example, a fine pattern having a width of 5 to 20 nm, the composition can be used in a photoresist process using light in a wavelength range of 5 to 150 nm, for example, a photoresist process using light in a wavelength range of 5 to 100 nm, for example, a photoresist process using light in a wavelength range of 5 to 80 nm, for example, a photoresist process using light in a wavelength range of 5 to 50 nm, for example, a photoresist process using light in a wavelength range of 5 to 30 nm, for example, a photoresist process using light in a wavelength range of 5 to 20 nm. Therefore, by using the semiconductor photoresist composition according to one embodiment of the present invention, extreme ultraviolet lithography using an EUV light source with a wavelength of 13.5 nm can be realized.
また、本発明の他の一実施形態によれば、上述した半導体フォトレジスト用組成物を使用してパターンを形成する方法を提供することができる。一例として、製造されたパターンは、フォトレジストパターンであり得る。より具体的には、ネガティブ型フォトレジストパターンであり得る。 According to another embodiment of the present invention, a method for forming a pattern using the above-mentioned semiconductor photoresist composition can be provided. As an example, the pattern produced can be a photoresist pattern. More specifically, it can be a negative type photoresist pattern.
本発明の一実施形態によるパターン形成方法は、基板上にエッチング対象膜を形成する工程、前記エッチング対象膜上に前述した半導体フォトレジスト用組成物を塗布してフォトレジスト膜を形成する工程、前記フォトレジスト膜をパターニングしてフォトレジストパターンを形成する工程、および前記フォトレジストパターンをエッチングマスクとして用いて前記エッチング対象膜をエッチングする工程を含む。 A method for forming a pattern according to one embodiment of the present invention includes the steps of forming a film to be etched on a substrate, applying the above-described semiconductor photoresist composition onto the film to be etched to form a photoresist film, patterning the photoresist film to form a photoresist pattern, and etching the film to be etched using the photoresist pattern as an etching mask.
以下、上述した半導体フォトレジスト用組成物を使用してパターンを形成する方法について、図1~5を参照しながら説明する。図1~5は、本発明による半導体フォトレジスト用組成物を用いたパターン形成方法を説明するための断面概略図である。 The method for forming a pattern using the above-mentioned semiconductor photoresist composition will be described below with reference to Figures 1 to 5. Figures 1 to 5 are schematic cross-sectional views for explaining the pattern formation method using the semiconductor photoresist composition according to the present invention.
図1を参照すると、まずエッチング対象物を設ける。エッチング対象物の例としては、半導体基板100上に形成される薄膜102であり得る。以下では、エッチング対象物が薄膜102の場合に限り説明する。薄膜102上に残留する汚染物などを除去するために、薄膜102の表面を洗浄する。薄膜102は、例えばシリコン窒化膜、ポリシリコン膜またはシリコン酸化膜であり得る。 Referring to FIG. 1, first, an object to be etched is provided. An example of the object to be etched may be a thin film 102 formed on a semiconductor substrate 100. In the following, only the case where the object to be etched is the thin film 102 will be described. The surface of the thin film 102 is cleaned to remove contaminants remaining on the thin film 102. The thin film 102 may be, for example, a silicon nitride film, a polysilicon film, or a silicon oxide film.
次に、洗浄された薄膜102の表面上に、レジスト下層膜104を形成するためのレジスト下層膜形成用組成物を、スピンコート方式を適用してコートする。ただし、本発明の実施形態は、必ずしもこれに限定されるものではなく、公知の多様なコート方法、例えばスプレーコート、ディップコート、ナイフエッジコート、印刷法、例えばインクジェット印刷およびスクリーン印刷などを用いることもできる。 Next, a resist underlayer film forming composition for forming a resist underlayer film 104 is applied to the surface of the cleaned thin film 102 by spin coating. However, the embodiment of the present invention is not necessarily limited to this, and various known coating methods such as spray coating, dip coating, knife edge coating, and printing methods such as inkjet printing and screen printing can also be used.
レジスト下層膜をコートする工程は省略することができ、以下ではレジスト下層膜をコートする場合について説明する。 The process of coating the resist underlayer film can be omitted, and the following describes the case where the resist underlayer film is coated.
その後、乾燥およびベーキング工程を行って、薄膜102上にレジスト下層膜104を形成する。ベーキング処理は、100~500℃で行い、例えば100~300℃で行い得る。 Then, a drying and baking process is performed to form a resist underlayer film 104 on the thin film 102. The baking process is performed at 100 to 500°C, for example, 100 to 300°C.
レジスト下層膜104は、基板100とフォトレジスト膜106との間に形成され、基板100とフォトレジスト膜106との界面または層間ハードマスク(hardmask)から反射する照射線が意図されないフォトレジスト領域に散乱する場合、フォトレジスト線幅(linewidth)の不均一およびパターン形成性を妨げることを防止することができる。 The resist underlayer film 104 is formed between the substrate 100 and the photoresist film 106, and can prevent the non-uniformity of the photoresist linewidth and the disruption of pattern formability when radiation reflected from the interface between the substrate 100 and the photoresist film 106 or from the interlayer hard mask is scattered into unintended photoresist regions.
図2を参照すると、レジスト下層膜104の上に上述した半導体フォトレジスト用組成物をコートして、フォトレジスト膜106を形成する。フォトレジスト膜106は、基板100上に形成された薄膜102の上に、上述した半導体フォトレジスト用組成物をコートした後、熱処理工程により硬化した形態であり得る。 Referring to FIG. 2, the above-mentioned semiconductor photoresist composition is coated on the resist underlayer film 104 to form a photoresist film 106. The photoresist film 106 may be in a form in which the above-mentioned semiconductor photoresist composition is coated on the thin film 102 formed on the substrate 100 and then hardened by a heat treatment process.
より具体的には、半導体フォトレジスト用組成物を使用してパターンを形成する工程は、上述した半導体レジスト用組成物を薄膜102が形成された基板100上にスピンコート、スリットコート、インクジェット印刷などで塗布する工程、および塗布された半導体フォトレジスト用組成物を乾燥してフォトレジスト膜106を形成する工程を含み得る。 More specifically, the process of forming a pattern using the semiconductor photoresist composition may include a process of applying the above-mentioned semiconductor resist composition onto the substrate 100 on which the thin film 102 has been formed by spin coating, slit coating, inkjet printing, or the like, and a process of drying the applied semiconductor photoresist composition to form a photoresist film 106.
半導体フォトレジスト用組成物については既に詳細に説明したので、重複する説明は省略する。 The composition for semiconductor photoresist has already been explained in detail, so we will not repeat the explanation here.
次に、フォトレジスト膜106が形成されている基板100を加熱する第1ベーキング工程を行う。第1ベーキング工程は80~120℃の温度で行い得る。 Next, a first baking process is performed to heat the substrate 100 on which the photoresist film 106 is formed. The first baking process can be performed at a temperature of 80 to 120°C.
図3を参照すると、フォトレジスト膜106を選択的に露光する。 Referring to FIG. 3, the photoresist film 106 is selectively exposed to light.
露光工程で使用できる光の例としては、i-線(波長365nm)、KrFエキシマレーザー(波長248nm)、ArFエキシマレーザー(波長193nm)などの短波長を有する光だけでなく、EUV(Extreme UltraViolet;波長13.5nm)、E-Beam(電子線)などの高エネルギー波長を有する光などが挙げられる。 Examples of light that can be used in the exposure process include light with short wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), as well as light with high energy wavelengths such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam).
より具体的には、本発明の一実施形態による露光用の光は、5~150nmの波長範囲を有する短波長光であり得、EUV(Extreme UltraViolet;波長13.5nm)、E-Beam(電子線)などの高エネルギー波長を有する光であり得る。 More specifically, the light for exposure according to one embodiment of the present invention may be short-wavelength light having a wavelength range of 5 to 150 nm, or may be light having a high-energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm) or E-Beam (electron beam).
上記フォトレジストパターンを形成する工程において、ネガティブ型パターンを形成することができる。 In the process of forming the photoresist pattern, a negative type pattern can be formed.
フォトレジスト膜106のうち、露光領域106aは、有機金属化合物間の縮合などの架橋反応によって重合体を形成することにより、フォトレジスト膜106の未露光領域106bと互いに異なる溶解度を有するようになる。 The exposed regions 106a of the photoresist film 106 form a polymer through a crosslinking reaction such as condensation between organometallic compounds, and thus have a different solubility from the unexposed regions 106b of the photoresist film 106.
次に、基板100に第2ベーキング工程を行う。第2ベーキング工程は90~200℃の温度で行い得る。第2ベーキング工程を行うことによって、フォトレジスト膜106の露光領域106aは、現像液に溶解し難い状態となる。 Next, the substrate 100 is subjected to a second baking process. The second baking process can be performed at a temperature of 90 to 200°C. By performing the second baking process, the exposed region 106a of the photoresist film 106 becomes less soluble in a developer.
図4には、現像液を用いて、未露光領域に該当するフォトレジスト膜106bを溶解させて除去することによって形成されたフォトレジストパターン108が示されている。具体的には、プロピレングリコールモノメチルエーテルアセテート(PGMEA)などの有機溶媒を使用して、未露光領域に該当するフォトレジスト膜106bを溶解させた後除去することによって、ネガティブトーンイメージに該当するフォトレジストパターン108が完成される。 FIG. 4 shows a photoresist pattern 108 formed by dissolving and removing the photoresist film 106b corresponding to the unexposed region using a developer. Specifically, the photoresist film 106b corresponding to the unexposed region is dissolved and then removed using an organic solvent such as propylene glycol monomethyl ether acetate (PGMEA), thereby completing the photoresist pattern 108 corresponding to a negative tone image.
上記で説明したように、本発明の一実施形態によるパターン形成方法で使用される現像液は有機溶媒であり得る。一実施形態によるパターン形成方法で使用される有機溶媒の例としては、例えば、メチルエチルケトン、アセトン、シクロヘキサノン、2-ヘプタノンなどのケトン類、4-メチル-2-プロパノール、1-ブタノール、イソプロパノール、1-プロパノール、メタノールなどのアルコール類、プロピレングリコールモノメチルエーテルアセテート、エチルアセテート、エチルラクテート、n-ブチルアセテート、ブチロラクトンなどのエステル類、ベンゼン、キシレン、トルエンなどの芳香族化合物、またはこれらの組み合わせが挙げられる。 As described above, the developer used in the pattern formation method according to one embodiment of the present invention may be an organic solvent. Examples of organic solvents used in the pattern formation method according to one embodiment include ketones such as methyl ethyl ketone, acetone, cyclohexanone, and 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, and methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, and butyrolactone, aromatic compounds such as benzene, xylene, and toluene, or combinations thereof.
上記で説明したように、i-線(波長365nm)、KrFエキシマレーザー(波長248nm)、ArFエキシマレーザー(波長193nm)等の波長を有する光だけでなく、EUV(Extreme UltraViolet;波長13.5nm)、E-Beam(電子線)などの高エネルギーを有する光などによって露光されて形成されたフォトレジストパターン108は、5~100nm厚さの幅を有することができる。上記フォトレジストパターン108は、5~90nm、5~80nm、5~70nm、5~60nm、5~50nm、5~40nm、5~30nm、5~20nmの厚さの幅で形成され得る。 As described above, the photoresist pattern 108 formed by exposure to light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5 nm) and E-Beam (electron beam) can have a thickness of 5 to 100 nm. The photoresist pattern 108 can be formed with a thickness of 5 to 90 nm, 5 to 80 nm, 5 to 70 nm, 5 to 60 nm, 5 to 50 nm, 5 to 40 nm, 5 to 30 nm, or 5 to 20 nm.
一方、上記フォトレジストパターン108は、50nm以下、例えば40nm以下、例えば30nm以下、例えば20nm以下、例えば15nm以下のハーフピッチ(half-pitch)および、10nm以下、5nm以下、3nm以下、2nm以下の線幅粗さを有するピッチを有することができる。 On the other hand, the photoresist pattern 108 may have a half-pitch of 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and a pitch with a line width roughness of 10 nm or less, 5 nm or less, 3 nm or less, 2 nm or less.
次に、上記フォトレジストパターン108をエッチングマスクとして、上記レジスト下層膜104をエッチングする。上記のようなエッチング工程により有機膜パターン112が形成される。形成された上記有機膜パターン112も、フォトレジストパターン108に対応する幅を有することができる。 Next, the resist underlayer film 104 is etched using the photoresist pattern 108 as an etching mask. The organic film pattern 112 is formed by the above-described etching process. The formed organic film pattern 112 may also have a width corresponding to the photoresist pattern 108.
図5を参照すると、フォトレジストパターン108をエッチングマスクに適用して、露出した薄膜102をエッチングする。その結果、薄膜102は薄膜パターン114として形成される。 Referring to FIG. 5, the photoresist pattern 108 is applied as an etching mask to etch the exposed thin film 102. As a result, the thin film 102 is formed as a thin film pattern 114.
薄膜102のエッチングは、例えばエッチングガスを使用した乾式エッチングで行うことができる。エッチングガスは、例えばCHF3、CF4、Cl2、BCl3およびこれらの混合ガスを使用することができる。 The thin film 102 can be etched by dry etching using, for example, an etching gas such as CHF 3 , CF 4 , Cl 2 , BCl 3 or a mixture thereof.
EUV光源を使用して行われた露光工程によって形成されたフォトレジストパターン108を用いて形成された薄膜パターン114は、フォトレジストパターン108に対応する幅を有することができる。例として、フォトレジストパターン108と同様に5~100nmの幅を有することができる。例えば、EUV光源を使用して行われた露光工程によって形成された薄膜パターン114は、フォトレジストパターン108と同様に、5~90nm、5~80nm、5~70nm、5~60nm、5~50nm、5~40nm、5~30nm、5~20nmの幅を有することができ、より具体的には20nm以下の幅で形成され得る。 The thin film pattern 114 formed using the photoresist pattern 108 formed by the exposure process performed using an EUV light source may have a width corresponding to the photoresist pattern 108. For example, it may have a width of 5 to 100 nm, similar to the photoresist pattern 108. For example, the thin film pattern 114 formed by the exposure process performed using an EUV light source may have a width of 5 to 90 nm, 5 to 80 nm, 5 to 70 nm, 5 to 60 nm, 5 to 50 nm, 5 to 40 nm, 5 to 30 nm, 5 to 20 nm, similar to the photoresist pattern 108, and more specifically may be formed with a width of 20 nm or less.
以下、上述した半導体フォトレジスト用組成物の製造に関する実施例により本発明をさらに詳細に説明する。しかし、本発明の技術的特徴は、下記の実施例によって限定されるものではない。 The present invention will be described in more detail below with reference to examples relating to the production of the above-mentioned semiconductor photoresist composition. However, the technical features of the present invention are not limited to the following examples.
合成例1:有機スズ化合物1の合成
下記化学式A-1で表される化合物(10g、25.6mmol)に25mlの酢酸を常温でゆっくり滴下した後、110℃で24時間加熱還流した。
Synthesis Example 1: Synthesis of organotin compound 1 To a compound represented by the following chemical formula A-1 (10 g, 25.6 mmol), 25 ml of acetic acid was slowly added dropwise at room temperature, and the mixture was heated under reflux at 110° C. for 24 hours.
その後、温度を常温に下げ、酢酸を真空蒸留して、下記化学式B-1で表される有機スズ化合物1を得た(収率:90%)。 Then, the temperature was lowered to room temperature, and the acetic acid was vacuum distilled to obtain organotin compound 1 represented by the following chemical formula B-1 (yield: 90%).
合成例2:有機スズ化合物2の合成
下記化学式A-2で表される化合物(10g、25.4mmol)に、25mlのアクリル酸を常温でゆっくり滴下した後、110℃で24時間加熱還流した。
Synthesis Example 2: Synthesis of organotin compound 2 To a compound (10 g, 25.4 mmol) represented by the following chemical formula A-2, 25 ml of acrylic acid was slowly added dropwise at room temperature, and the mixture was heated to reflux at 110°C for 24 hours.
その後、温度を常温に下げ、アクリル酸を真空蒸留して、下記化学式B-2で表される有機スズ化合物2を得た(収率:50%)。 Then, the temperature was lowered to room temperature, and the acrylic acid was vacuum distilled to obtain organotin compound 2 represented by the following chemical formula B-2 (yield: 50%).
合成例3:有機スズ化合物3の合成
下記化学式A-3で表される化合物(10g、23.7mmol)に、25mlのプロピオン酸を常温でゆっくり滴下した後、110℃で24時間加熱還流した。
Synthesis Example 3: Synthesis of organotin compound 3 To a compound (10 g, 23.7 mmol) represented by the following chemical formula A-3, 25 ml of propionic acid was slowly added dropwise at room temperature, and the mixture was heated to reflux at 110°C for 24 hours.
その後、温度を常温に下げ、プロピオン酸を真空蒸留して、下記化学式B-3で表される有機スズ化合物3を得た(収率:95%)。 Then, the temperature was lowered to room temperature, and the propionic acid was vacuum distilled to obtain organotin compound 3 represented by the following chemical formula B-3 (yield: 95%).
合成例4:有機スズ化合物4の合成
上記合成例2の化学式A-2で表される化合物(10g、25.4mmol)に、25mlのイソブチル酸を常温でゆっくり滴下した後、110℃で24時間加熱還流した。
Synthesis Example 4 Synthesis of Organotin Compound 4 To the compound represented by chemical formula A-2 in Synthesis Example 2 above (10 g, 25.4 mmol), 25 ml of isobutyric acid was slowly added dropwise at room temperature, and the mixture was heated to reflux at 110° C. for 24 hours.
その後、温度を常温に下げ、イソブチル酸を真空蒸留して、下記化学式B-4で表される有機スズ化合物4を得た(収率:95%)。 Then, the temperature was lowered to room temperature, and the isobutyric acid was vacuum distilled to obtain organotin compound 4 represented by the following chemical formula B-4 (yield: 95%).
合成例5:有機スズ化合物5の合成
下記化学式A-4で表される化合物(10g、24.6mmol)に、25mlのプロピオン酸を常温でゆっくり滴下した後、110℃で24時間加熱還流した。
Synthesis Example 5: Synthesis of organotin compound 5 To a compound (10 g, 24.6 mmol) represented by the following chemical formula A-4, 25 ml of propionic acid was slowly added dropwise at room temperature, and the mixture was heated to reflux at 110°C for 24 hours.
その後、温度を常温に下げ、プロピオン酸を真空蒸留して、下記化学式B-5で表される有機スズ化合物5を得た(収率:90%)。 Then, the temperature was lowered to room temperature, and the propionic acid was vacuum distilled to obtain organotin compound 5 represented by the following chemical formula B-5 (yield: 90%).
実施例1~7
合成例1~5で得られた有機スズ化合物それぞれに対して、下記表1に示した有機酸化合物を混合した後、PGMEA(5質量%脱イオン水を含む、Propylene glycol methyl ether acetate)を添加し、固形分20質量%の濃度の溶液を製造した。
Examples 1 to 7
The organotin compounds obtained in each of Synthesis Examples 1 to 5 were mixed with the organic acid compounds shown in Table 1 below, and then PGMEA (propylene glycol methyl ether acetate containing 5% by mass of deionized water) was added to prepare solutions with a solid content of 20% by mass.
上記溶液を80℃で24時間攪拌した後常温に冷まし、追加のPGMEAで固形分が3質量%になるように希釈し、下記実施例1~7による縮合物含有溶液を製造した。その後、0.1μm PTFE(ポリテトラフルオロエチレン)シリンジフィルタ(syringe filter)で濾過してフォトレジスト組成物を製造した。 The above solution was stirred at 80°C for 24 hours, cooled to room temperature, and diluted with additional PGMEA to a solid content of 3% by mass to prepare a condensate-containing solution according to Examples 1 to 7 below. The solution was then filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare a photoresist composition.
比較例1~5
合成例1~5で得られた有機スズ化合物を、それぞれPGMEAに固形分3質量%の濃度で溶かし、0.1μm PTFE(ポリテトラフルオロエチレン)製シリンジフィルタ(syringe filter)で濾過して、フォトレジスト組成物を製造した。
Comparative Examples 1 to 5
Each of the organotin compounds obtained in Synthesis Examples 1 to 5 was dissolved in PGMEA to a solid content concentration of 3 mass % and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) syringe filter to prepare a photoresist composition.
評価1:感度およびラインエッジ粗さ(LER)の評価
実施例1~7および比較例1~5による組成物を円形のシリコンウェハー上に1500rpmで30秒間スピンコーティングして得られたフィルムを、40nm Half-pitchのナノ線パターンが形成されるように、100kV加速電圧の極端紫外線(E-beam)に露光させた。露光した薄膜を、170℃で60秒間ベーキングした後、2-heptanoneが入ったペトリ皿に30秒間浸漬して取り出した。その後、同一の溶剤で10秒間洗浄した。最終的に、150℃で180秒間ベーキングした後、FE-SEM(field emission scanning electron microscopy)によりパターンイメージを得た。FE-SEMイメージから確認された形成された線のCD(Critical Dimension)サイズおよびラインエッジ粗さ(LER)を測定した後、下記基準により感度およびラインエッジ粗さを評価して、下記表2に示した。
Evaluation 1: Evaluation of Sensitivity and Line Edge Roughness (LER) The compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 were spin-coated on a circular silicon wafer at 1500 rpm for 30 seconds to obtain a film, which was then exposed to extreme ultraviolet light (E-beam) at an accelerating voltage of 100 kV so that a 40 nm half-pitch nanoline pattern was formed. The exposed thin film was baked at 170° C. for 60 seconds, and then immersed in a Petri dish containing 2-heptanone for 30 seconds and removed. It was then washed with the same solvent for 10 seconds. Finally, the film was baked at 150° C. for 180 seconds, and a pattern image was obtained by FE-SEM (field emission scanning electron microscopy). The CD (Critical Dimension) size and line edge roughness (LER) of the formed lines confirmed from the FE-SEM images were measured, and the sensitivity and line edge roughness were evaluated according to the following criteria, and the results are shown in Table 2 below.
※評価基準
(1)感度
1000uC/cm2エネルギーで測定されたCDサイズを、下記基準により評価してその結果を表2に示す:
◎:40nm以上
○:35nm以上40nm未満
△:35nm未満
×:パターンが確認されない。
Evaluation criteria (1) Sensitivity The CD size measured at an energy of 1000 uC/ cm2 was evaluated according to the following criteria, and the results are shown in Table 2:
⊚: 40 nm or more; ◯: 35 nm or more and less than 40 nm; Δ: less than 35 nm; ×: no pattern is observed.
(2)ラインエッジ粗さ(LER)
○:4nm以下
△:4nm超7nm以下
×:7nm超。
(2) Line Edge Roughness (LER)
◯: 4 nm or less △: more than 4 nm and less than 7 nm ×: more than 7 nm.
評価2:保存安定性の評価
一方、上述した実施例1~7および比較例1~5によるフォトレジスト組成物について、下記のような基準として保存安定性を評価し、下記表2に示した:
[保存安定性]
常温(20±5℃)条件で、実施例1~7および比較例1~5によるフォトレジスト組成物を特定期間放置した時、沈殿が発生する程度を肉眼で観察し、下記の保存可能な基準により2段階で評価した:
※評価基準
○:6ヶ月以上保存可能
△:3ヶ月以上6ヶ月未満保存可能
×:6ヶ月未満保存可能。
Evaluation 2: Evaluation of Storage Stability Meanwhile, the storage stability of the photoresist compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 was evaluated according to the following criteria, and the results are shown in Table 2 below:
[Storage stability]
The photoresist compositions according to Examples 1 to 7 and Comparative Examples 1 to 5 were left at room temperature (20±5° C.) for a certain period of time, and the degree of precipitation was observed with the naked eye and evaluated on a two-level scale according to the following storage criteria:
*Evaluation criteria: ◯: Can be stored for 6 months or more; △: Can be stored for 3 months or more but less than 6 months; ×: Can be stored for less than 6 months.
表2を参照すると、実施例1~7による半導体フォトレジスト用組成物は、比較例1~5に比べて、保存安定性においてさらに優れることが分かり、半導体フォトレジスト用組成物を用いて形成されたパターンも、実施例1~7の場合が比較例1~5に対してさらに優れた感度およびラインエッジ粗さ(LER)を示すことを確認することができる。 Referring to Table 2, it can be seen that the semiconductor photoresist compositions of Examples 1 to 7 have better storage stability than Comparative Examples 1 to 5, and it can also be seen that the patterns formed using the semiconductor photoresist compositions of Examples 1 to 7 show better sensitivity and line edge roughness (LER) than Comparative Examples 1 to 5.
以上、本発明の特定の実施例を説明し図示したが、本発明は記載された実施例に限定されるものではなく、本発明の思想および範囲を逸脱せず多様に修正および変形できることはこの技術の分野で通常の知識を有する者に自明である。したがって、このような修正例または変形例は本発明の技術的思想や観点から個別に理解されてはならず、変形した実施例は本発明の特許請求範囲に属するといえる。 Although specific embodiments of the present invention have been described and illustrated above, the present invention is not limited to the described embodiments, and it will be obvious to those of ordinary skill in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, such modifications or variations should not be understood individually from the technical spirit and perspective of the present invention, and the modified embodiments can be said to fall within the scope of the claims of the present invention.
100 基板、
102 薄膜、
104 レジスト下層膜、
106 フォトレジスト膜、
106a 露光領域、
106b 未露光領域、
108 フォトレジストパターン、
112 有機膜パターン、
114 薄膜パターン。
100 substrate,
102 thin film,
104 resist underlayer film,
106 Photoresist film,
106a exposure area,
106b unexposed area;
108 Photoresist pattern,
112 organic film pattern,
114 Thin film pattern.
Claims (6)
溶媒を含む、半導体フォトレジスト用組成物:
前記化学式1において、
R1は、非置換の炭素数1~20のアルキル基であり、
Ra、Rb、およびRcは、それぞれ独立して、非置換の炭素数1~20のアルキル基、または非置換の炭素数2~20のアルケニル基である。 A composition obtained by mixing and heating an organotin compound represented by the following chemical formula 1 and at least one organic acid compound selected from the group consisting of glycolic acid, malonic acid, succinic acid, and 1,2,3,4-butanetetracarboxylic acid ; and a composition for semiconductor photoresist, comprising :
In the above Chemical Formula 1,
R 1 is an unsubstituted alkyl group having 1 to 20 carbon atoms;
R a , R b , and R c are each independently an unsubstituted alkyl group having 1 to 20 carbon atoms , or an unsubstituted alkenyl group having 2 to 20 carbon atoms.
前記エッチング対象膜上に、請求項1または2に記載の半導体フォトレジスト用組成物を塗布してフォトレジスト膜を形成する工程;
前記フォトレジスト膜をパターニングしてフォトレジストパターンを形成する工程;および
前記フォトレジストパターンをエッチングマスクとして用いて、前記エッチング対象膜をエッチングする工程、
を含む、パターン形成方法。 forming a film to be etched on a substrate;
A step of forming a photoresist film by applying the semiconductor photoresist composition according to claim 1 or 2 onto the film to be etched;
patterning the photoresist film to form a photoresist pattern; and etching the film to be etched using the photoresist pattern as an etching mask.
A pattern forming method comprising:
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020200178620A KR102598259B1 (en) | 2020-12-18 | 2020-12-18 | Semiconductor photoresist composition and method of forming patterns using the composition |
KR10-2020-0178620 | 2020-12-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2022097388A JP2022097388A (en) | 2022-06-30 |
JP7482846B2 true JP7482846B2 (en) | 2024-05-14 |
Family
ID=81992496
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2021183873A Active JP7482846B2 (en) | 2020-12-18 | 2021-11-11 | Semiconductor photoresist composition and pattern formation method using the same |
Country Status (5)
Country | Link |
---|---|
US (1) | US12013635B2 (en) |
JP (1) | JP7482846B2 (en) |
KR (1) | KR102598259B1 (en) |
CN (1) | CN114647146A (en) |
TW (1) | TWI776738B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102619719B1 (en) * | 2020-05-12 | 2023-12-28 | 삼성에스디아이 주식회사 | Semiconductor photoresist composition and method of forming patterns using the composition |
KR102598259B1 (en) | 2020-12-18 | 2023-11-02 | 삼성에스디아이 주식회사 | Semiconductor photoresist composition and method of forming patterns using the composition |
JP7390348B2 (en) * | 2020-12-18 | 2023-12-01 | 三星エスディアイ株式会社 | Composition for semiconductor photoresist, method for producing the same, and pattern forming method using the same |
IL305619A (en) * | 2022-09-14 | 2024-04-01 | Shinetsu Chemical Co | Compound for forming metal-containing film, composition for forming metal-containing film, patterning process, and semiconductor photoresist material |
WO2024128013A1 (en) * | 2022-12-16 | 2024-06-20 | Jsr株式会社 | Composition for forming resist underlayer film, method for producing semiconductor substrate, method for forming resist underlayer film and method for producing metal compound |
JP2024089633A (en) * | 2022-12-21 | 2024-07-03 | 信越化学工業株式会社 | Polymer for forming metal-containing film, composition for forming metal-containing film, and method for forming pattern |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020021071A (en) | 2018-07-31 | 2020-02-06 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Semiconductor resist composition, and method of forming patterns using the same |
JP2020184074A (en) | 2019-04-30 | 2020-11-12 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Semiconductor photoresist composition and method of forming patterns using the composition |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2832750A (en) * | 1951-06-21 | 1958-04-29 | Metal & Thermit Corp | Organo tin compounds, method of making same, and mixtures thereof with halogen-containing resins |
NL88419C (en) * | 1953-01-22 | 1900-01-01 | ||
US5061599A (en) | 1986-06-11 | 1991-10-29 | Hitachi, Ltd. | Radiation sensitive materials |
KR950001702B1 (en) | 1992-04-16 | 1995-02-28 | 한국과학기술연구원 | Organotinmalonates derivatives, and process for their preparation |
JP3180629B2 (en) | 1994-12-09 | 2001-06-25 | 三菱マテリアル株式会社 | Composition for forming metal oxide thin film pattern, method for manufacturing the same, method for forming metal oxide thin film pattern, and method for manufacturing electronic components and optical components |
KR100386719B1 (en) | 1996-12-19 | 2004-05-22 | 주식회사 코오롱 | Diazo type of photosensitive film |
KR100269513B1 (en) | 1997-10-08 | 2000-10-16 | 윤덕용 | New acrylate or metacrylate derivatives and photoresist containing its polymer |
KR20010045418A (en) | 1999-11-05 | 2001-06-05 | 박종섭 | Novel photoresist monomer, polymer thereof and photoresist composition containing it |
KR100398312B1 (en) | 2000-06-30 | 2003-09-19 | 한국과학기술원 | Organometal-containing norbornene monomer, photoresist containing its polymer, manufacturing methods thereof, and method of forming photoresist patterns |
EP1209527A1 (en) | 2000-11-28 | 2002-05-29 | Shipley Company LLC | Photoresist composition |
KR20020047490A (en) | 2000-12-13 | 2002-06-22 | 윤종용 | Photosensitive polymer containing silicon and resist composition comprising the same |
JP5124077B2 (en) | 2003-03-03 | 2013-01-23 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | Polymer and photoresist containing the same |
JP4831324B2 (en) | 2006-07-06 | 2011-12-07 | 日産化学工業株式会社 | Resist underlayer film forming composition containing sulfone |
KR20110137400A (en) | 2006-11-01 | 2011-12-22 | 더 스테이트 오브 오레곤 액팅 바이 앤드 쓰루 더 스테이트 보드 오브 하이어 에쥬케이션 온 비해프 오브 오레곤 스테이트 유니버시티 | Solution processed thin films and laminates, devices comprising such thin films and laminates, and method for their use and manufacture |
JP2009229593A (en) | 2008-03-19 | 2009-10-08 | Mitsuboshi Belting Ltd | Ink composition for repairing photomask, and photomask repairing method |
US9176377B2 (en) | 2010-06-01 | 2015-11-03 | Inpria Corporation | Patterned inorganic layers, radiation based patterning compositions and corresponding methods |
JP5708521B2 (en) | 2011-02-15 | 2015-04-30 | 信越化学工業株式会社 | Resist material and pattern forming method using the same |
JP5650086B2 (en) | 2011-06-28 | 2015-01-07 | 信越化学工業株式会社 | Resist underlayer film forming composition and pattern forming method |
US8703386B2 (en) | 2012-02-27 | 2014-04-22 | International Business Machines Corporation | Metal peroxo compounds with organic co-ligands for electron beam, deep UV and extreme UV photoresist applications |
US9310684B2 (en) | 2013-08-22 | 2016-04-12 | Inpria Corporation | Organometallic solution based high resolution patterning compositions |
KR101486533B1 (en) | 2013-09-16 | 2015-02-09 | 한국기계연구원 | Method for manufacturing quantum dot and method for manufacturing solar cell using the same |
CN105934485B (en) * | 2014-01-24 | 2019-04-09 | 株式会社日本触媒 | Dispersion containing metal oxide particle |
EP4050014A3 (en) | 2014-10-23 | 2022-12-14 | Inpria Corporation | Organometallic solution based high resolution patterning compositions |
US9499698B2 (en) | 2015-02-11 | 2016-11-22 | Az Electronic Materials (Luxembourg)S.A.R.L. | Metal hardmask composition and processes for forming fine patterns on semiconductor substrates |
JP6666572B2 (en) | 2015-03-05 | 2020-03-18 | Jsr株式会社 | Radiation-sensitive composition and pattern forming method |
JP6202228B2 (en) | 2015-04-01 | 2017-09-27 | 東レ株式会社 | Photosensitive resin composition, method for producing conductive pattern, substrate, touch panel and display |
EP3085661B1 (en) | 2015-04-21 | 2017-12-27 | JSR Corporation | Method of producing microfluidic device |
JP6774814B2 (en) | 2015-08-20 | 2020-10-28 | 国立大学法人大阪大学 | Chemically amplified resist material and pattern forming method |
US10228618B2 (en) * | 2015-10-13 | 2019-03-12 | Inpria Corporation | Organotin oxide hydroxide patterning compositions, precursors, and patterning |
KR20180121550A (en) | 2016-03-28 | 2018-11-07 | 제이에스알 가부시끼가이샤 | A radiation-sensitive composition and a method for forming a pattern |
JP2017207532A (en) | 2016-05-16 | 2017-11-24 | 東洋合成工業株式会社 | Resist composition and method for producing device using the same |
JP2018017780A (en) | 2016-07-25 | 2018-02-01 | Jsr株式会社 | Radiation-sensitive composition and pattern formation method |
TWI804224B (en) | 2016-08-12 | 2023-06-01 | 美商英培雅股份有限公司 | Methods of reducing metal residue in edge bead region from metal-containing resists |
WO2018043506A1 (en) | 2016-08-29 | 2018-03-08 | Jsr株式会社 | Radiation sensitive composition and pattern forming method |
ES2841406T3 (en) | 2016-09-07 | 2021-07-08 | Ivoclar Vivadent Ag | Polymerizable compositions with acyltin photoinitiators |
KR102493962B1 (en) | 2016-10-19 | 2023-02-01 | 롬엔드하스전자재료코리아유한회사 | Photosensitive resin composition and cured film prepared therefrom |
JPWO2018084050A1 (en) | 2016-11-07 | 2019-09-26 | 東洋合成工業株式会社 | Metal-containing onium salt compound, photodegradable base, resist composition, and device manufacturing method using the resist composition |
WO2018168221A1 (en) | 2017-03-13 | 2018-09-20 | Jsr株式会社 | Radiation sensitive composition and pattern forming method |
WO2018179704A1 (en) | 2017-03-27 | 2018-10-04 | Jsr株式会社 | Pattern forming method |
CA2975104A1 (en) | 2017-08-02 | 2019-02-02 | Seastar Chemicals Inc. | Organometallic compounds and methods for the deposition of high purity tin oxide |
JP7070935B2 (en) | 2017-11-17 | 2022-05-18 | 三井化学株式会社 | Semiconductor device intermediates, metal-containing film forming compositions, semiconductor device intermediate manufacturing methods, semiconductor device manufacturing methods |
WO2019099981A2 (en) * | 2017-11-20 | 2019-05-23 | Inpria Corporation | Organotin clusters, solutions of organotin clusters, and application to high resolution patterning |
TW201942323A (en) | 2018-03-30 | 2019-11-01 | 日商住友化學股份有限公司 | Mixed composition |
US11287740B2 (en) | 2018-06-15 | 2022-03-29 | Taiwan Semiconductor Manufacturing Co., Ltd. | Photoresist composition and method of forming photoresist pattern |
KR102296793B1 (en) | 2018-07-06 | 2021-08-31 | 삼성에스디아이 주식회사 | Semiconductor resist composition, and method of forming patterns using the composition |
US11092889B2 (en) * | 2018-07-31 | 2021-08-17 | Samsung Sdi Co., Ltd. | Semiconductor resist composition, and method of forming patterns using the composition |
KR20200014185A (en) | 2018-07-31 | 2020-02-10 | 삼성에스디아이 주식회사 | Semiconductor resist composition, and method of forming patterns using the composition |
KR102306444B1 (en) | 2018-07-31 | 2021-09-28 | 삼성에스디아이 주식회사 | Semiconductor resist composition, and method of forming patterns using the composition |
US11092890B2 (en) | 2018-07-31 | 2021-08-17 | Samsung Sdi Co., Ltd. | Semiconductor resist composition, and method of forming patterns using the composition |
KR102307977B1 (en) | 2018-07-31 | 2021-09-30 | 삼성에스디아이 주식회사 | Semiconductor resist composition, and method of forming patterns using the composition |
KR102307981B1 (en) | 2018-08-10 | 2021-09-30 | 삼성에스디아이 주식회사 | Semiconductor resist composition, and method of forming patterns using the composition |
US11215924B2 (en) | 2018-08-31 | 2022-01-04 | Taiwan Semiconductor Manufacturing Co., Ltd. | Photoresist, developer, and method of forming photoresist pattern |
US20200326627A1 (en) * | 2019-04-12 | 2020-10-15 | Inpria Corporation | Organometallic photoresist developer compositions and processing methods |
KR102606844B1 (en) | 2019-04-30 | 2023-11-27 | 삼성에스디아이 주식회사 | Semiconductor resist composition and method of forming patterns using the composition |
KR102555497B1 (en) * | 2020-01-21 | 2023-07-12 | 삼성에스디아이 주식회사 | Semiconductor resist composition and method of forming patterns using the composition |
KR102573327B1 (en) | 2020-04-02 | 2023-08-30 | 삼성에스디아이 주식회사 | Semiconductor photoresist composition and method of forming patterns using the composition |
KR102619719B1 (en) * | 2020-05-12 | 2023-12-28 | 삼성에스디아이 주식회사 | Semiconductor photoresist composition and method of forming patterns using the composition |
KR102598259B1 (en) | 2020-12-18 | 2023-11-02 | 삼성에스디아이 주식회사 | Semiconductor photoresist composition and method of forming patterns using the composition |
-
2020
- 2020-12-18 KR KR1020200178620A patent/KR102598259B1/en active IP Right Grant
-
2021
- 2021-11-10 US US17/454,453 patent/US12013635B2/en active Active
- 2021-11-11 JP JP2021183873A patent/JP7482846B2/en active Active
- 2021-11-17 CN CN202111360348.8A patent/CN114647146A/en active Pending
- 2021-11-22 TW TW110143319A patent/TWI776738B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020021071A (en) | 2018-07-31 | 2020-02-06 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Semiconductor resist composition, and method of forming patterns using the same |
JP2020184074A (en) | 2019-04-30 | 2020-11-12 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Semiconductor photoresist composition and method of forming patterns using the composition |
Also Published As
Publication number | Publication date |
---|---|
US20220197138A1 (en) | 2022-06-23 |
KR102598259B1 (en) | 2023-11-02 |
US12013635B2 (en) | 2024-06-18 |
TWI776738B (en) | 2022-09-01 |
KR20220088013A (en) | 2022-06-27 |
JP2022097388A (en) | 2022-06-30 |
CN114647146A (en) | 2022-06-21 |
TW202225178A (en) | 2022-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7482846B2 (en) | Semiconductor photoresist composition and pattern formation method using the same | |
JP7390348B2 (en) | Composition for semiconductor photoresist, method for producing the same, and pattern forming method using the same | |
JP2021179606A (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
JP2024010648A (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
JP7486641B2 (en) | Composition for semiconductor photoresist and method for forming pattern using the same | |
KR102690557B1 (en) | Semiconductor photoresist composition, method for preparing thereof and method of forming patterns using the composition | |
KR102586109B1 (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
TWI795899B (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
JP2023175620A (en) | Semiconductor photoresist composition and method of forming patterns using the same | |
KR102678333B1 (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
KR102671848B1 (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
KR102586110B1 (en) | Semiconductor photoresist composition, and method of forming patterns using the composition | |
JP2024072786A (en) | Composition for semiconductor photoresist and method for forming pattern using the same | |
KR20240047829A (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
JP2024096665A (en) | Composition for semiconductor photoresist and method for forming pattern using the same | |
JP2024068122A (en) | Composition for semiconductor photoresist and method for forming pattern using the same | |
KR20240040479A (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
KR20240038462A (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
TW202307145A (en) | Composition for removing edge beads from metal-containing resists and method of forming patterns | |
KR20230160087A (en) | Semiconductor photoresist composition and method of forming patterns using the composition | |
KR20230023410A (en) | Semiconductor photoresist composition and method of forming patterns using the composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20211111 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221026 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20221115 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230207 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230530 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230830 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231205 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240301 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240423 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240430 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7482846 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |